Biodegradable sulfonate detergents

ABSTRACT

Novel compositions of matter which are useful as biodegradable detergents may be prepared by condensing butadiene with allyl chloride, thereafter ring alkylating the resultant chloromethylcyclohexene with an olefin in the presence of a freeradical generating compound and thereafter reacting the disubstituted cyclohexene with an alkali metal salt of a sulfurcontaining compound to form an alkali metal di-substituted cyclohexenyl sulfate or sulfonate.

United States Patent Bloch Feb. 18, 1975 BIODEGRADABLE SULFONATEDETERGENTS [75] Inventor: Herman S. Bloch, Skokie, Ill.

[73] Assignee: Universal Oil Products Company, Des Plaines, Ill.

[22] Filed: Aug. 3, 1972 [2]] Appl. No.: 277,837

[52] US. Cl 260/503, 260/458, 252/549 [51] Int. Cl. C07c 143/00 [58]Field of Search 260/503 [56] References Cited UNITED STATES PATENTS3,168,555 2/1965 Clippinger et al. 260/503 Primary ExaminerLeon ZitverAssistant ExaminerA. Siegel Attorney, Agent, or FirmJames R. Hoatson,Jr.; Raymond H. Nelson; William H. Page, II

[57] ABSTRACT Novel compositions of matter which are useful asbiodegradable detergents may be prepared by condensing butadiene withallyl chloride, thereafter ring alkylating the resultantchloromethylcyclohexene with an olefin in the presence of a free-radicalgenerating compound and thereafter reacting the di-substitutedeyclohexene with an alkali metal salt of a sulfur-containing compound toform an alkali metal di-substituted cyclohexenyl sulfate or sulfonate.

2 Claims, N0 Drawings 1 B IODEGRADABLE SULFONATE DETERGENTS Thisinvention relates to novel compositions of matter and to a process forpreparing these compounds which are useful as biodegradable detergents.More specifically the invention is concerned with these compounds and toa novel method comprising a series of steps whereby alkali metal saltsof di-substituted cyclohexene or cyclohexane sulfates or sulfonateswhich are biodegradable in nature are formed.

One of the major problems which is prevalent in population centersthroughout the world is the disposal of sewage containing detergentsdissolved therein. Such disposal problems are especially trying in thecase of branched chained alkylaryl detergents. These detergents producestable foams in hard or soft waters in such large quantities that thefoam clogs sewage treatment facilities, and destroys the bacteria whichare necessary for proper sewage treatment. In many rivers, streams,lakes, etc. which act as a water supply for the aforesaid populationcenters, there are found these unwanted foams and suds. As hereinbeforeset forth the presence of these unwanted foams or suds is due in manyinstances to the use of detergents which are nonbiodegradable in natureand which will not break down by bacterial action thereon. Thenon-biodegradable nature of these detergents is due to the fact that thealkyl I side chain of the molecule is in many instances highly branchedand therefore not readily attacked by the organisms which wouldordinarily destroy the molecule. In contradistinction to this, the useof straight chain alkyl substituents on the ring will permit thedetergents to be destroyed and therefore foams or suds will not build upon the surface of the water.

It is therefore an object of this invention to provide a novel methodfor the manufacture of biodegradable detergents which may be degraded inboth urban and rural sewage disposal systems.

A further object of this invention is to provide novel compositions ofmatter comprising biodegradable detergents.

In one aspect an embodiment of this invention resides in a compounduseful as a biodegradable detergent selected from the group consistingof:

CH2S03M RCH CH RCHZCH 2 2 and CH20S03M RCHZCHZ in which M is an alkalimetal and R is an alkyl group of from 1 to about 14 carbon atoms.

Another embodiment of this invention is found in a process for thepreparation of a biodegradable detergent which comprises the steps of:(a) condensing butadiene with allyl chloride at condensation conditions,(b) alkylating the resulting chloromethylcyclohexene with an olefin inthe presence of a free-radical generating compound and hydrogen chlorideat a temperature at least as high as the decomposition temperature ofsaid free-radical generating compound, and (c) reacting the resultingalkyl-substituted chloromethylcyclohexene with an alkali metal salt of asulfurcontaining compound, and recovering the resultant alkali metalsalt of a di-substituted cyclohexyl or cyclohexenyl sulfate orsulfonate.

A specific embodiment of this invention is found in a biodegradabledetergent such as sodium (noctylcyclohexenyl) methano sulfonate.

Another specific embodiment of this invention is found in a process forthe preparation of a biodegradable detergent which comprises condensingbutadiene with allyl chloride at a temperature in the range of fromabout 50 to about 190 C. at a pressure in the range of from aboutatmospheric to about atmospheres, alkylating the resultantchloromethylcyclohexene with l-octene in the presence of di-t-butylperoxide and hydrogen chloride at a temperature at least as high as thedecomposition temperature of said di-t-butyl peroxide and reacting theresultant compound with sodium sulfite at a temperature in the range offrom 50 to about C. and recovering the resultant sodium (n-octyl-3-cyclohexenyl) methano sulfonate.

Other objects and embodiments will be found in the following furtherdetailed description of the present invention.

As hereinbefore set forth the present invention is concerned with novelcompositions of matter and to a process for the preparation of thesecompounds which are useful as biodegradable detergents, the processbeing effected in a series of steps. In the first step of the reactionbutadiene is reacted with allyl chloride in a Diels-Alder typecondensation to give 4-chloromethylcyclohexene. l-lomologs of butadiene,such as isoprene, or analogous cyclic conjugated dienes such ascyclopentadiene or cyclohexadiene may be used instead of butadiene, andthese yield generally similar results, but butadiene is preferred. TheDiels-Alder condensation is effected at elevated temperatures usually inthe range CH OSO M M 3 CH SO RCH CH pressure which is utilized beingthat which is sufficient to maintain at least a portion of the reactantsin the H9219 Ph s The 4-c hloromethylcyclohexene which has been preparedaccording to the above paragraph is then selectively alkylated utilizingan olefinic hydrocarbon as the alkylating agent. The selectivealkylation in which the alkyl substituent is positioned on the ringrather than on the side chain is effected by treating the reactants inthe presence of a free-radical generating compound and hydrogenchloride. in the preferred embodiment of the invention the olefinichydrocarbon which is utilized as the alkylating agent will comprise ana-olefin containing from about 3 to about 20 carbon atoms. By utilizingan alkylation catalyst comprising a free-radical generating compound anda promoter comprising hydrogen chloride, it is possible to obtain anormal alkyl side chain on the cyclohexene ring rather than a secondaryalkyl side chain which would result if the alkylation were effected inthe presence of an acidic catalyst of the Friedel-Crafts type orsulfuric acid, etc. Specific examples of these olefmic hydrocarbonswhich are utilized as alkylating agents include l-hexene, l-heptene,l-octene, l-nonene, l-decene, l-undecene, 1- dodecene, l-tridecene,l-tetradecene, etc. It is also contemplated within the scope of thisinvention that other a-olefins containing less than 6 or more than 14carbon atoms may also be utilized, said olefins including propene,l-butene, l-pentene, l-pentadecene, 1- hexadecene, l-heptadecene,l-octadecene, 1- nonadecene, l-eicosene, etc.

The catalysts which are used in this step of the invention will includeperoxy compounds, containing the bivalent radical -O, which decomposesto form free radicals which initiate the general reaction and arecapable of inducing the condensation of the chloromethylcyclohexene withthe l-alkene. Examples of these catalysts include the persulfates,perborates, percarbonates of ammonium and of the alkali metals, ororganic peroxy compounds. The organic peroxy compounds constitute apreferred class of catalysts for use in the invention and includeperacetic acid, persuccinic acid, methyl ethyl ketone peroxide, methylisobutyl ketone peroxide, acetyl peroxide, dipropionyl peroxide,di-t-butyl peroxide, butyryl peroxide, lauroyl peroxide, benzoylperoxide, tetralin peroxide, urea peroxide, tbutyl perbenzoate, t-butylhydroperoxide, methylcyclohexyl hydroperoxide, cumene hydroperoxide,diisopropylbenzene hydroperoxide, etc. Mixtures of peroxy compoundcatalysts may be employedor the peroxy compound catalyst may be utilizedin admixture with various diluents. Thus, organic peroxy compounds whichare compounded commercially with various diluents which 'may be usedinclude benzoyl peroxide compounded with calcium sulfate, benzoylperoxide compounded with camphor, phthalate esters, etc. Only catalyticamounts (less than stoichiometric amounts) need be used in the process.

The alkylation of the chloromethylcyclohexene with the l-alkene iseffected at elevated reaction temperatures which should be at least ashigh as the initial decomposition temperature of the free-radicalgenerating ergy by means of heat must be supplied to the reaction sothat the reactants, namely the chloromethylcyclohexene and the l-alkeneswill be activated sufficiently for condensation to take place when freeradicals are generated by the catalyst. Second, free-radical generatingcatalysts such as peroxy compounds, particularly organic peroxides,decompose at a measurable rate with time in a logarithmic functiondependent upon temperature. This rate of decomposition can be andordinarily is expressed as the half life of a peroxide at a particulartemperature. For example, the half life in hours for di-t-butyl peroxideis 11 hours at 125 C., 4 hours at 135 C., and 1.5 hours at 145 C. Areaction system temperature must then be selected so that thefree-radical generating catalyst decomposes smoothly with the-generationof free radicals at a half life which is not too long. In other words,sufficient free radicals must be present to induce the present chainreaction to take place, and these radicals must be formed at atemperature at which the reactants are in a suitably activated state forcondensation. When the half life of the free-radical generating catalystis greater than 10 hours, radicals are not generated at a sufficientrate to cause the reaction of the process of the present invention to goforward at a practically useful rate. Thus the reaction temperature maybe within the range of from about to about 300 C. and at least as highas the decomposition temperature of the catalyst, by which is meant atemperature such that the half life of the freeradical generatingcatalyst is not greater than 10 hours. Since the half life for eachfree-radical generating catalyst is different at different temperatures,the exact temperature to be utilized in a particular reaction will vary.However, persons skilled in the art are well acquainted with the halflife vs. temperature data for different free-radical generatingcatalysts. Thus it is within the skill of one familiar with the art toselect the particular temperature needed for any particular catalyst.However, the operating temperatures generally do not exceed thedecomposition temperature of the catalyst by more than about 100 C.since free-radical generating catalysts decompose rapidly under suchconditions.

. For example, when a free-radical generating catalyst such as t-butylperbenzoate is used, having a 50% decomposition temperature (in 10hours) of approxi mately C., the operating temperature of the process isfrom about 105 to about 205 C. When di-tbutyl peroxide having a 10 hour,50% decomposition temperature of about C. is used, the process is run ata temperature ranging from about 125 to about 225 C. Higher reactiontemperatures may be employed, but little advantage is gained if thetemperature is more than the hereinbefore mentioned 100 C. higher thanthe 10 hour, 50% decomposition temperature of the catalyst. The generaleffect of increasing the operating temperature is to accelerate the rateof condensation reaction of the chloromethylcyclohexene and the 1-alkene. However, the increased rate of reaction is accompanied bycertain amounts of decomposition. In addition to the elevatedtemperatures which are utilized, the reaction may also be effected atelevated pressures ranging from about 1 to about 100 atmospheres ormore, thepreferred operating pressure of the process being that which isrequired to maintain a substantial portion of the reactants in liquidphase. Pressure is not an important variable in the process of thisinvention. However, because of the low boiling points of some of thereactants it is necessary to utilize pressure-withstanding equipment toinsure liquid phase conditions. In batch type operations, it is oftendesirable to utilize pressure-withstanding equipment, to charge thereactants and the catalyst to the vessel and to pressure the vessel withor 30 or 50 or more atmospheres of an inert gas such as nitrogen. Thishelps to insure the presence of liquid phase conditions. However, whenthe mole quantity of reactants is sufficient, the pressure which theythemselves generate at the temperature utilized is sufficient tomaintain the desired phase conditions.

Furthermore, the concentration of the catalyst employed in this processmay vary over a rather wide range but it is desirable to utilize lowconcentrations of catalysts such as from about 0.1% to about 10% of thetotal weight of the combined starting materials charged to the process.The reaction time may be within the range of from less than 1 minute toseveral hours, depending upon temperature and the half life of thecatalyst. Generally speaking, contact times of at least 10 minutes arepreferred.

In addition to the free-radical generating catalyst the alkylation isalso effected in the presence of a hydrogen chloride compound. Thehydrogen chloride compound is used as a promoter for the reaction andalso is used to prevent or inhibit telomerization, said telomerizationbeing a polymerization reaction in which unwanted side reaction productsmay be formed. The hydrogen chloride may be present as anhydroushydrogen chloride, as concentrated hydrochloric acid or as an aqueoussolution of hydrochloric acid, the hydrochloric acid being present in anamount of from 5% to about 38% in said aqueous solution. 7

An alternative method which may be employed in preparing the novelcompositions of matter of the present invention which comprisebiodegradable detergents is to submit the chloromethylcyclohexene to ahydrogenation step prior to alkylating the compound with a terminalolefin in the presence of a free-radical generating catalyst andhydrogen chloride as set forth in the preceding paragraphs. When suchalternative method is followed, the chloromethylcyclohexene isselectively hydrogenated in the presence of a noble metal catalyst,these hydrogenation catalysts being well-known in the art. Specificexamples of these catalysts will include in particular platinum andpalladium compounds per se or composited on a solid support which isessentially nonacidic in character such as charcoal or kieselguhr. Thereaction is effected at hydrogenation conditions which will include atemperature in the range of from about 25 to about 50 C. and at anapplied hydrogen pressure which may range from 50 to about 2,000 poundsper square inch whereby the chloromethyl substituent remains unchangedwhile the cyclohexene ring is hydrogenated to form a cyclohexane ring.Thereafter, the chloromethylcyclohexane may be subjected to a ringalkylation by reaction with an a-olefin in the presence of theaforementioned free-radical generating compounds and hydrogen chloride.In an alternative variation of this procedure, the hydrogenation of thering unsaturation may be carried out after the alkylation of thechloromethylcyclohexene, ie on the n-alkyl substitutedchloromethylcyclohexene.

The resulting di-substituted cyclohexane comprising an n-alkylchloromethylcyclohexane or n-alkyl chloromethylcyclohexene is thereafterreacted with an alkali metal salt of a sulfur-containing compound suchas an alkali sulfite, alkali bisulfite, alkali sulfate, or alkalibisulfate. Representative examples of these alkali metal salts willinclude sodium sulfite, sodium bisulfite, sodium sulfate, sodiumbisulfate, potassium sulfite, potassium bisulfite, potassium sulfate,potassium bisulfate, lithium sulfite, lithium bisulfite, lithiumsulfate, lithium bisulfate, rubidium sulfite, rubidium bisulfite,rubidium sulfate, rubidium bisulfate, cesium sulfite, cesium bisulfite,cesium sulfate, cesium bisulfate, etc., the preferred compoundscomprising the sodium or potassium salts due to their relatively lowercost and greater availability. The reaction is usually effected atelevated temperatures in the range of from about 50 to about C. or moreand at atmospheric pressure. Preferably the sulfonation is effected inthe presence of a high dielectric solvent, said solvents includingdimethyl sulfoxide, dimethylformamide, dioxane, etc.

The process of this invention in which the novel compositions of matteruseful as biodegradable detergents are prepared may be effected ineither a batch type or continuous type of operation. When a batch typeoperation is used, a quantity of the allyl chloride is placed in anappropriate apparatus such as an autoclave and butadiene is chargedthereto. The autoclave is then heated to the desired operatingtemperature and pressure in the range hereinbefore set forth andmaintained thereat for a predetermined residence time which may rangefrom about 0.5 up to about 10 hours or more in duration. Upon completionof the desired residence time, heating is discontinued, the autoclave isallowed to return to room temperature, the excess pressure is vented andthe reaction mixture is recovered. The 4-chloromethylcyclohexene isseparated from any unreacted allyl chloride by conventional means suchas distillation or any other separation means known in the art andplaced in a second reaction vessel along with a free'radical generatingcompound and the l-alkene which is to be utilized as the alkylatingagent. In addition, a promoter comprising hydrogen chloride either ingaseous form as hydrogen chloride or in aqueous form as hydrochloricacid is added to the reactor which is thereafter heated to the desiredoperating temperature which, as hereinbefore set forth, is at least ashigh as the decomposition temperature of said free-radical generatingcompound. After maintaining the alkylation reaction at this temperaturefor a predetermined period of time, heating is discontinued, thereaction mixture is allowed to return to room temperature and thealkylsubstituted chloromethylcyclohexene is again recovered byconventional means.

Alternatively, the 4-chloromethylcyclohexene may be subjected to ahydrogenation step prior to alkylation with the l-alkene. If this stepis to be employed, the chloromethylcyclohexene is selectivelyhydrogenated by passage over a catalyst such as a platinum orpalladium-containing compound in the presence of a hydrogen stream at atemperature and pressure within the range hereinbefore set forth, thecyclohexene ring being selectively and relatively completelyhydrogenated to form a cyclohexane ring. After separation from thehydrogen gas, the chloromethylcyclohexane is then subjected toalkylation with the l-alkene according to the method hereinbefore setforth. The n-alkyl chloromethylcyclohexane or n-alkylchloromethylcyclohexene is then reacted with the alkali metal salt of asulfur-containing compound at elevated temperatures and in the presenceof a solvent of the type hereinbefore set forth. Following thesulfonation step which may take again from about 0.5 up to about 10hours or more, heating is discontinued, the desired product is separatedfrom the solvent by fractionation and passed to storage.

It is also contemplated within the scope of this invention that thedesired product may be prepared while employing a continuous type ofoperation. When the continuous type of operation is to be used, thestarting materials comprising the allyl chloride and butadiene arecontinuously charged to a reactor which is maintained at the properoperating conditions of temperature and pressure. After passage throughthis reactor, the effluent is continuously withdrawn, subjected to aseparation step whereby the unreacted allyl chloride and butadiene areseparated from the chloromethylcyclohexene and recycled to form aportion of the feed stock while the latter is continuously charged to analkylation apparatus which is also maintained at the proper operatingconditions of temperature and pressure. ln addition the l-alkene, thefree-radical generating compound and the hydrogen chloride promoter arealso continuously charged to this alkylation apparatus CH2S03M Z ZRCH2CH2 and 'CH2'0SO3M IRCHZCHZ through separate lines. After completingthe desired residence time in the alkylation apparatus, the reactoreffluent is continuously withdrawn, againsubjected to separation stepswhereby unreacted starting materials, promoter and free-radicalgenerating compound are separated from the alkyl-substitutedchloromethylcyclohexene. The unreacted materials are recycled to form aportion of the feed stock to the apparatus while the alkyl-substitutedchloromethylcyclohexene is continuously charged to a sulfonationreactor. The alkali metal sulfur-containing compound such as sodiumsulfate, sodium bisulfate, etc. is continuously charged to thesulfonation reactor along with the solvent. The solvent may be chargedto the reactor through a separate line or one or both of the reactantsmay be admixed with the solvent prior to entry into said reactor and theresulting mixture charged thereto in a single stream. After completionof the desired residence time in the sulfonation reactor the effluent isagain continuously In the event that the desired biodegradable detergentcomprises a di-substituted cyclohexane, the product resulting from theDiels-Alder condensation between allyl chloride and butadiene issubjected to selective hydrogenation prior to the alkylation step withthe lalkene. The 4-chloromethylcyclohexene which is with drawn from thefirst condensation apparatus, after being separated from unreacted allylchloride and butadiene, is continuously charged to a hydrogenationapparatus along with a stream of hydrogen sufficient to maintain thedesired operating pressure. The hydrogen and 4-chloromethylcyclohexeneare continuously passed over a hydrogen catalyst of the typehereinbefore set forth at a temperature in the range of from about 25 toabout 50 C. and the resulting product is continuously withdrawn. Theproduct which has been selectively and usually relatively completelyhydrogenated to form chloromethylcyclohexane is thereafter charged tothe alkylation reactor previously described.

Some specific examples of the novel compositions of matter which may beprepared according to the process herein set forth will include thosecompounds having the generic formula:

CH 0S0 M H S0 M RCH (n-undecyl-3-cyclohexenyl) methano sulfonate, so--dium (n-tetradecyl-3-cyclohexenyl) methano sulfonate, sodium(n-propyl-3-cyclohexenyl) methano sulfate, sodium(n-butyl-3-cyclohexenyl) methano sulfate, sodium(n-pentyl-3-cyclohexenyl) methano sulfate, sodium(n-hexyl-3-cyclohexenyl) methano sulfate, sodium(n-heptyl-3-cyclohexenyl) methano sulfate, sodium(n-octyl-3-cyclohexenyl) methano sulfate, sodium(n-decyl-3-cyclohexenyl) methano sulfate, sodium(n-undecyl-3-cyclohexenyl) methano sulfate, sodium(n-tetradecyl-3-cyclohexenyl) methano sulfate, potassium(n-propyl-3-cyclohexenyl) methano sulfonate, potassium(n-pentyl-3-cyclohexenyl) methano.

sulfonate, potassium (n-heptyl-3-cyclohexenyl) methano sulfonate,potasium (n-decyl-B-cyclohexenyl) methano sulfonate, potassium(n-tctradccyl-3- cyclohexenyl) methano sulfonate, lithium (n-butyl-3-cyclohexenyl) methano sulfonate, lithium (n-hexyl-3- cyclohexenyl)methano sulfonate, lithium (n-octyl-3- cyclohexenyl) methano sulfonate,lithium (n-undecyl- 3-cyclohexenyl) methano sulfonate, etc. It is to beunderstood that the aforementioned biodegradable detergents are onlyrepresentative of the novel class of com-.

EXAMPLE I In this example 76.5 g. (1.0 mole) of allyl chloride is placedin the glass liner of a rotating autoclave. The liner is sealed into theautoclave and 54 g. (1.0 mole) of butadiene is charged thereto. Theautoclave is then heated to a temperature of 125 C. and maintainedthereat for a period of 4 hours. At the end of this time, heating isdiscontinued and the autoclave is allowed to return to room temperature.The autoclave is opened and the reaction mixture is recovered therefrom.Following this, the mixture is subjected to fractional distillationwhereby the desired product comprising 4-chloromethylcyclohexene isseparated from any unreacted allyl chloride and recovered.

The 4-chloromethylcyclohexene which is prepared according to the aboveparagraph is then placed in the glass liner of a rotating autoclavealong with l-octene, the charge stock usually consisting of a molarexcess of the chloromethylcyclohexene over the l-octene is a range offrom about 1.5:1 to about 2:1 moles of chloromethylcyclohexene per moleof l-octene. In addition, 7 g. of di-t-butyl peroxide and g. ofconcentrated hydrochloric acid are placed in the autoclave. Theautoclave is sealed and nitrogen is pressed in until an initialoperating pressure of atmospheres is reached. The autoclave and contentsthereof are then -heated to a temperature of 130 C. and maintainedthereat for a period of 8 hours. At the end of the 8-hour period,heating is discontinued, the autoclave is allowed to return to roomtemperature and the excess pressure is discharged therefrom. Theautoclave is opened, the reaction mixture is recovered and subjected tofractional distillation, usually under reduced pressure, whereby thedesired product comprising n-octyl-3-cyclohexenylmethyl chloride isrecovered.

The n-octyl-3-cyclohexenylmethyl chloride which is prepared according tothe above paragraph is then sulfonated by placing said compound in aflask along with an equimolar amount of sodium sulfite and a solventcomprising dimethyl sulfoxide. The flask is then heated to a temperatureof 50 C. The reaction mixture is maintained at this temperature for aperiod of 4 hours. At the end of this time, heating is discontinued.Upon cooling, the reaction mixture is separated from the solvent and anyunreacted starting materials, the desired product comprising sodium(n'octyl-3-cycl0hexenyl) methano sulfonate being recovered therefrom.

EXAMPLE II In this example a mole proportion of allyl chloride is placedin the glass liner of a rotating autoclave. The au- 10 toclave issealed, a mole proportion of butadiene along with a sufficient amount ofnitrogen is pressed in until an initial operating pressure of 30atmospheres is reached. The autoclave and contents thereof are thenheated to a temperature of C. and maintained in a range of 130 to C. fora period of 4 hours. At the end of the 4-hour period, heating isdiscontinued, the autoclave is allowed to return to room temperature andthe excess pressure is discharged therefrom. The autoclave is opened andthe reaction mixture is recovered and subjected to fractionaldistillation-under reduced pressure whereby the desired productcomprising 4-chloromethylcyclohexene is separated and recovered.

The which is prepared according to the above paragraph is then placed inanother liner of a rotating autoclave along with l-tetradecene, thechloromethylcyclohexene being present in a molar excess over thetetradecene. In addition a catalyst comprising di-t-butyl peroxide and apromoter comprising concentrated hydrochloric acid is also added to theliner. The liner is then sealed into the autoclave and nitrogen ispressed in until an initial operating pressure of 30 atmospheres isreached. The autoclave and contents thereof are then heated to atemperature of 130 C. and maintained in a range of from 130 to 140 C.for a period of 8 hours. At the end of the 8-hour period, heating isdiscontinued, the autoclave is allowed to return to room temperature,the excess pressure is discharged and the autoclave is opened. Thereaction mixture is subjectedto fractional distillation under reducedpressure whereby the desired n-tetradecyl-3-cyclohexenylmethyl chlorideis recovered. I

As in the above example this di-substituted cyclohexene is reacted in amolar proportion with sodium sulfate, said reaction being effected inthe presence of a solvent comprising dimethyl sulfoxide at a temperatureof about 60 C. for a period of 4 hours. At the end of the 4-hour period,heating is discontinued, the reaction mixture is again subjected tofractional distillation under reduced pressure whereby the desiredproduct comprising sodium (n-tetradecyl-3-cyclohexyl) methano sulfate isrecovered.

EXAMPLE III In this example 4-chloromethylcyclohexene is prepared in amanner similar to that hereinbefore set forth. The thus preparedchloromethylcyclohexene is charged to a reactor which is loaded with acatalyst comprising platimum composited on granular charcoal, saidcharge being effected at a temperature which is maintained below 50 C.The chloromethylcyclohexene is charged to the reactor at a liquid hourlyspace velocity of 0.5 along with a stream of hydrogen in an amountsufficient to maintain a hydrogen pressure of 1000 pounds per squareinch. After passage over the catalyst the effluent stream is withdrawnto a separation zone whereby the hydrogen gas is separated from theorganic liquid phase. Bromine number determinations on the product showthat aproximately 95% comprises the desired product,chloromethylcyclohexane.

The chloromethylcyclohexane which is prepared according to the aboveparagraph is then placed in the glass liner of a rotating autoclavealong with l-octene, a catalyst comprising di-t-butyl peroxide andconcentrated hydrochloric acid, the chloromethylcyclohexane'aforementioned 4-chloromethylcyclohexene being in a molar excess overthe l-octene. The autoclave is sealed and nitrogen is pressed in untilan initial operating pressure of 30 atmospheres is reached, after whichthe autoclave is heated to a temperature of 130 C. The autoclave ismaintained at a temperature in the range of from about 130 to 140 C. fora period of 8 hours, following which heating is discontinued, theautoclave is allowed to return to room temperature and the excesspressure is discharged therefrom. The autoclave is opened, the reactionproduct is recovered and subjected to conventional means of separationwhereby the n-octyl substituted chloromethylcyclohexane is separated andrecovered.

The n-octyl substituted chloromethylcyclohexane is then treated in amanner similar to that hereinbefore set forth with sodium sulfite at atemperature of about 60 C. in the presence of a solvent comprisingdimethyl sulfoxide, for a period of 4 hours; At the end of this time,heating is discontinued, the mixture is recovered and subjected toconventional means of separation whereby the desired product comprisingsodium (noctyl-3-cyclohexyl) methano sulfonate is separated andrecovered.

EXAMPLE IV In this example 4-chloromethylcyclohexene is prepared in amanner similar to that hereinbefore set forth.

The thus prepared 4-chloromethylcyclohexene which results from thecondensation in a Diels-Alder manner between butadiene and allylchloride is then charged to, a reactor which has been loaded with ahydrogenation catalyst comprising palladium composited on kieselguhr.The 4-chloromethylcyclohexene is charged to the reactor at a temperatureof about 40 C., a liquid hourly space velocity of 0.5 along with astream of hydrogen sufficient to maintain a hydrogen pressure of 2000pounds per square inch. After passage over the catalyst the effluentstream is withdrawn to a separation zone whereby the hydrogen gas isseparated from the liquid phase. This liquid phase is found to compriseover 90% of the desired product, chloromethylcyclohexane.

The aforementioned chloromethylcyclohexane along with l-tetradecene,benzoyl peroxide and concentrated hydrochloric acid are placed in analkylation apparatus and heated to reflux at a temperature in the rangeof from about 80 to 85 C. for a period of 4 hours. At the end of the4-hour period, heating is discontinued and the reactor is allowed toreturn to room temperature. The reaction mixture is recovered, subjectedto distillation whereby the desired product comprising ntetradecylsubstituted chloromethylcyclohexane is recovered. The n-tetradecylsubstituted chloromethylcyclohexane is then reacted with sodium sulfateat a temperature of about 75 C. for a period of 4 hours in the presenceof a solvent comprising 1,4-dioxane. At the end of the 4-hour period,heating is discontinued, and the reaction mixture is allowed to cool toroom temperature. After cooling to room temperature the mixture issubjected to conventional means of separation whereby the desiredproduct comprising sodium (n-tetradecylcyclohexyl) methano sulfate isrecovered.

EXAMPLE v To the glass liner of a rotating autoclave is charged 76.5 g.(1.0 mole) of allyl chloride and thereafter the liner is sealed into theautoclave. Following this 54 g. (1.0 mole) of butadiene is chargedthereto and the autoclave is heated to a temperature of C. Aftermaintaining the autoclave at this temperature for a period of 4 hours,heating is discontinued and the autoclave is allowed to return to roomtemperature. The autoclave is opened and the reaction mixture issubjected to fractional distillation whereby the desired4-chloromethylcyclohexene is separated from any unreacted allyl chlorideand recovered.

The 4-chloromethylcyclohexene which is thus prepared is placed in theglass liner of a rotating autoclave along with l-octene, saidchloromethylcyclohexene being in a molar excess over the l-octene. Inaddition to the starting materials, 7 g. of di-t-butyl peroxide and 20g. of concentrated hydrochloric acid are also placed in the autoclavewhich is thereafter sealed and pressured to an initial operatingpressure of 30 atmospheres with nitrogen. The autoclave and contentsthereof are then heated to a temperature of C. and maintained thereatfor a period of 8 hours, at the end of which time heating isdiscontinued and the autoclave is allowed to return to room temperature.The excess pressure is discharged, the autoclave is opened and thereaction mixture which is recovered therefrom is sub- I jected tofractional distillation under reduced pressure to separate and recovern-octyl-3-cyclohexenylmethyl chloride.

The aforementioned n-octyl-3-cyclohexenylmethyl chloride is sulfonatedby treating the compound with an equimolar amount of sodium sulfate inthe presence of a solvent comprising dimethyl sulfoxide, the reactionbeing effected at a temperature of 50 C. for a period of 4 hours. At theend of the 4-hour period, heating is discontinued and upon cooling, thereaction mixture is separated from the solvent and any unreactedstarting materials, the desired product comprising sodium(noctyl-3-cyclohexenyl) methano sulfate being recovered therefrom.

I claim as my invention:

1. A biodegradable detergent compound of the formula:

CH SO M RCH CH in which M is an alkali metal and R is an alkyl group offrom 1 to about 14 carbon atoms.

2. The biodegradable detergent compound sodium (n-octyl-3-cyclohexenyl)methano sulfonate.

1. A BIODEGRADABLE DETERGENT COMPOUND OF THE FORMULA:
 2. Thebiodegradable detergent compound sodium (n-octyl-3-cyclohexenyl) methanosulfonate.